The Art

1
The Art Science of Fragrance Flavor Creation
John C. Leffingwell

• Society of Flavor Chemists
• December 4, 2003

2
Fragrance Flavor Art Science

• Conventional Market View U.S. 15 Billion

3
Fragrance Flavor Art Science

• Conventional Market View U.S. 15 Billion

4
Fragrance Flavor Art Science

• Conventional Market View U.S. 15 Billion

5
Fragrance Flavor Art Science

• The Real Market U.S. 30 Billion

6
Fragrance Flavor Art Science

• Fragrance Flavor - The shaping of history

• Prehistory - Culinary Fragrant Oils
• Circa 7000 BC Fragrant plants and spices
  infused in the fatty oils of Olive Sesame for
  use as ointments

Earliest items of commerce were most likely
spices, gums and other fragrant plants.
7
Fragrance Flavor Art Science

• The shaping of history

• 3000 BC Indus Valley (Pakistan) - terra-cotta
  perfume containers and a primitive still - place
  it 3,000 years earlier than most sources date the
  invention of distillation.

• 3000 BC Egyptians when learning to write and
  make bricks, were already importing large
  quantities of myrrh.

8

Fragrance Flavor Art Science

• The shaping of history - Egypt

Perfume Vessel Symbolizing Unification - Reign of
Tutankhamon Calcite pots filled with spices such
as frankincense preserved in fat still gave off a
faint odor when opened in King Tutankhamen's tomb
after 3,000 years
9
Fragrance Flavor Art Science

• The shaping of history Greece

Greek Perfume Urns
By the 7th century BC, Athens had developed into
a mercantile center in which hundreds of
perfumers set up shop. Trade was heavy in
fragrant herbs such as marjoram, lily, thyme,
sage, anise, rose and iris, infused into olive,
almond, castor and linseed oils to make thick
unguents. These were sold in small, elaborately
decorated ceramic pots, similar to the small jars
still sold in Athens today.
10
Fragrance Flavor Art Science

• The shaping of history Greece circa 400 BC

Still of Democritus

• Leucippus and Democritus Fathers of the Atomic
  
• Theory

• The first firm documentary evidence of the
• distillation of essential oils is Herodotus'
  record
• of the method of distilling turpentine from
  425 B.C.

11
Fragrance Flavor Art Science

• The shaping of history Perfume basics - 300 BC

• Socrates classmate, Theophrastus, sent plant
  cuttings obtained during his extensive travels,
  thus establishing a botanical garden in Athens.
• Theophrastus' treatise On Odors covered all the
  basics blending perfumes, shelf life, using wine
  with aromatics, substances that carry scent, and
  the effect of odor on the mind and body.

12
Fragrance Flavor Art Science

• The shaping of history International Trade

• As trade routes expanded, Africa, South Arabia
  and India began to supply spikenard and ginger to
  Middle Eastern and Mediterranean civilization.
  Phoenician merchants traded in Chinese camphor
  and Indian cinnamon, pepper and sandalwood.
• True myrrh and frankincense from Yemen reached
  the Mediterranean by 300 BC, by way of Persian
  traders.
• Demand increased for roses, sweet flag, orris
  root, narcissus, saffron, mastic, oak moss,
  cinnamon, cardamom, pepper, nutmeg, ginger,
  costus, spikenard, aloewood, grasses and gum
  resins.

13
Fragrance Flavor Art Science

• The shaping of history Rome

By the 1st century AD, Rome was using about 2,800
tons of imported frankincense and 550 tons of
myrrh per year. Nero, Roman emperor in 54 AD,
spent the equivalent of 100,000 to scent just
one party he was giving. No Orgy was complete
without perfume.
14
Fragrance Flavor Art Science

• The Modern Toga Party

Former Tyco CEO Dennis Kozlowski Todays Nero
15
Fragrance Flavor Art Science

• The shaping of history Biblical Times

Fragrance occurs, at least symbolically,
throughout the New Testament. The frankincense
and myrrh brought to the Christ child were more
valuable than the gift of gold (if indeed it was
gold some speculate that the three wise men may
have been carrying gold-colored, fragrant
ambergris).
"Then took Mary a pound of ointment of spikenard,
very costly, and anointed the feet of Jesus, and
wiped his feet with her hair and the house was
filled with the odour of the ointment."John
123
16
Fragrance Flavor Art Science

• The shaping of history 1ST Century AD

Mary Prophetissa (Prophetissima) aka Maria the
Jewess
The tribokos
Invented the double boiler, also known as a Bain
Marie, or Mary's Bath as well as the first true
still which she called the tribokos.  It
consisted of copper tubing, ceramic pottery, and
metal.  When heated, vapors from plant material
and water would condense on the inside of the
still, then trickle down and collect in a bottle.
17
Fragrance Flavor Art Science

• The shaping of history 1ST Century AD

Mary Prophetissa (Prophetissima) aka Maria the
Jewess
Her design and many later modifications were used
to distill essential oils, but also proved useful
for alcoholic beverages. And with the still
dawned the new Age of Alchemy
18
Fragrance Flavor Art Science

• The shaping of history 10 -11th Century AD

Ibn Sina (Avicenna) a famous Arab physician and
alchemist that wrote over 400 books on medicine,
philosophy, geology, mathematics, astronomy, and
logic, is credited with significantly improving
the art of distillation by adding a water cooled
jacket around the cooling coil.
19
Fragrance Flavor Art Science

• The shaping of history 10-14th Century AD

• The Arabs used their new technique to distill
  ethyl alcohol (ethanol) from fermented sugar,
  providing a new solvent for the extraction of
  plant oils in place of the fatty oils that had
  been used for millennia.
• Knowledge of distillation gradually spread around
  Europe through trading and crusading until
  essential oils had become a specialty of
  mediaeval pharmacies.
• Essential oils were so-named because they were
  thought to represent the very essence of odor,
  flavor life. Their extraction was researched by
  alchemists in their search for the philosophers'
  stone that would turn common metals into gold.

20
Fragrance Flavor Art Science

• The shaping of history Marco Polo

• 1271 - Marco Polo, at the age of seventeen years,
  embarked from Venice with his father and uncle on
  a trip that would last 24 years and bring
  knowledge of the Orient and trade routes.
• Marco Polo lived for 16 years in China where he
  was employed for several years by Kublai Khan. He
  left China in 1292, returning to Venice (1295),
  and fought against the Genoese, but was captured.
  
• In prison he wrote of his adventures in 'Travels
  of Marco Polo' - a book which instantly fired the
  imagination of all Medieval Europe and spurred
  a competition among nations that would last 500
  years.

21
Fragrance Flavor Art Science

• The shaping of history Marco Polo

22
Fragrance Flavor Art Science

• The shaping of history Influence of Spice Trade

• In the 13th and 14th centuries, Italy monopolized
  the European Spice Perfume material trade that
  had begun during the Crusades.
• One purpose of Marco Polo's journey to China was
  to bypass Moslem middlemen and their 300 percent
  markup in price by convincing the Orient to trade
  directly with Venice.

23
Fragrance Flavor Art Science

• The shaping of history The Age of Exploration

• 1492 - Columbus discovered the Americas while
  looking for the spice islands of the Orient.
• Although, at the time, this failure was a great
  disappointment there were many treasures that
  resulted. Vast quantities of gold, silver as well
  as new culinary items such as chocolate (cocoa).
• New fragrant treasures such as Vanilla, balsam
  of Peru and Tolu, juniper, American cedar and
  sassafras soon became available to Europeans.

24
Fragrance Flavor Art Science

• The shaping of history Influence of Spice Trade

• 1497 - Vasco da Gama departs Lisbon Portugal to
  discover the sea passage to the distant spice
  Indies.
• 1498 - Vasco da Gama arrives in India by rounding
  Africa via the Cape of Good Hope and Portugal
  becomes the ruler of the Indian ocean for nearly
  150 years.

25
Fragrance Flavor Art Science

• The shaping of history The Age of Colonization

• 1602 - Dutch East India Company granted a
  monopoly on the trade in the East Indies.
• Purpose - trading spices like nutmeg, cloves,
  cinnamon and pepper, tea, silk and porcelain
• And to prevent other European nations from
  entering the East Indies for trade.
• Dec. 31, 1600 - Queen Elizabeth I grants a Royal
  Charter to the East India Company, but the Dutch
  massacre of the English at Amboyna in 1623
  reduced them initially to picking up scraps of
  trade, either by piracy or dealing with
  intermediaries.

26
Fragrance Flavor Art Science

• The shaping of history The Age of Colonization

• By the mid 1600s the Dutch had driven the
  British and Portuguese from Indonesia, Malaya,
  and Ceylon (Sri Lanka), and controlled the
  fabulous trade of the Spice Islands.
• 1621 - the Dutch started a West India Company,
  which established the American province of New
  Netherland in 1624, and reputedly purchased what
  is now New York from the Native Americans for the
  equivalent of 24.
• 1664 - the English capture New Netherland
• 1673 - New York was recaptured by a Dutch fleet
• 1674 The English negotiate peace and trade a
  small island off Indonesia (Rhun) for New York.

27
Fragrance Flavor Art Science

• The shaping of history Spice Wars

• New York traded for Rhun the best Nutmeg island

28
Fragrance Flavor Art Science
Quite A Trade
29
Fragrance Flavor Art Science

• The New Perfumers

• Perfumed leather gloves became popular in France
  and in 1656, the guild of glove and
  perfume-makers was established in Grasse. The use
  of perfume in France grew steadily. The court of
  Louis XV was even named the perfumed court.
• In 1732, when the Italian Giovanni Maria Farina
  took over his uncle's business in Cologne, he
  produced aqua admirabilis, a lively blend of
  neroli, bergamot, lavender and rosemary in
  rectified grape spirit. This was splashed on the
  skin, and also used for treating sore gums and
  indigestion. French soldiers later stationed
  there dubbed it eau de Cologne.

30
Fragrance Flavor Art Science

• The shaping of history France Perfume

16th 17th centuries - Southern France (Grasse)
becomes a center of expertise for the growing,
extraction and distillation of essential oils.
France becomes the the Perfume center of the
world. Large scale cultivation processing of
valuable plants for oils such as rose soon was
centered there. And raw materials from around the
world were imported for processing. Extraction
distillation techniques were refined.
31
Fragrance Flavor Art Science

• The shaping of history France Perfume

32
Fragrance Flavor Art Science

• Grasse France The Center of Perfumery

Perfume Factory - Grasse
Lavender field near Grasse
33
Fragrance Flavor Art Science

• The Perfumers Enfleurage process

• Flowers such as Jasmine are laid out on trays of
  fat that absorb the fragrance. The fat is later
  extracted with alcohol,and then concentrated into
  an absolute.

34
Fragrance Flavor Art Science

• The Production of Rose Oil

35
Fragrance Flavor Art Science

• The Production of Rose Oil

36
Fragrance Flavor Art Science

• The new partner The Organic Chemist

• Mid-1800s - From Germany came a new breed of
  Chemist that would revolutionize industry and
  bring an end to Alchemy. This type chemist
  used the scientific method to unravel chemical
  structures and create materials from coal,
  petroleum and other materials.
• 1855 First synthesis of cinnamaldehyde
• 1868 Commercial production of coumarin the
  first synthetic fragrance chemical
• 1874 Chemical structure of vanillin determined.
• 1876 Synthetic vanillin production starts.
• 1850 to 1900 Significant advances in
  elucidating
• major chemicals in Essential oils.

37
Fragrance Flavor Art Science

• The new partner The Organic Chemist

• Nobel Prize in Chemistry 1910 Otto Wallach

• Helps elucidate many of the C10H16 group terpene
  structures present in essential oils utilizing
  common reagents such as hydrogen chloride and
  hydrogen bromide. In 1909 he published the
  results of his extensive studies in the book
  Terpene und Campher, a volume of 600 pages
  dedicated to his pupils.

beta-Pinene
alpha-Pinene
Camphene
Camphor
38
Fragrance Flavor Art Science

• The new partner The Organic Chemist

• Nobel Prize in Chemistry 1939 - Leopold Ruzicka

• In the perfumery and sesquiterpene domain - the
  total
• syntheses of nerolidol and farnesol.
• From Jasmine - established the structure of
  jasmone.
• Elucidated the structures of the naturally
  occurring
• musk perfumes, civetone and muscone thus
  replacing
• scents prized since antiquity but only
  available from
• endangered species.

Civetone
Muscone
Musk Deer Moschus moschiferus L.
Civet Cat Viverra civetta
39
Fragrance Flavor Art Science

• The new partner The Organic Chemist

• Nobel Prize in Chemistry 2001 - Ryoji Noyori

• For chirally catalyzed hydrogenation reactions.
• In perfumery and flavors - the chiral
  (asymmetric)
• synthesis of Menthol many other fragrance
  flavor
• compounds.
• In the chiral synthesis of pharmaceutical
  photochromic
• materials.

40
Fragrance Flavor Art Science

• The new partner The Organic Chemist

• 1950s Bain Webb Turpentine into Fragrance
  Flavor

beta-Pinene
Linalool
Menthol
Linalyl Acetate
Myrcene
Geraniol
Citronellol
Citronellal
41
Fragrance Flavor Art Science

• Gas Chromatography Mass Spectrometry

Detective work
GC-MS analysis
Distillation extraction
Volatiles from a living flower
42
Fragrance Flavor Art Science

• Gas Chromatography Mass Spectrometry

GC-MS Analysis of a Meat Flavor
Abundance
Peak Identified as Furfuryl Mercaptan Powerful
Coffee Aroma
1.6e07
1.4e07
Peaks are 2-Methyl-2,3-dihydrofuran-3-thiol
isomers
Powerful meat-like aroma
1.2e07
1e07
8000000
6000000
4000000
2000000
0
12.00
14.00
16.00
18.00
20.00
22.00
24.00
26.00
28.00
30.00
32.00
34.00
36.00
Time--gt
43
Fragrance Flavor Art Science

• Gas Chromatography Mass Spectrometry

44
Fragrance Flavor Art Science

• Rose oil Whats Important

Concentration
Odor Unit
Odor Threshold

45
Fragrance Flavor Art Science

• Perfumery - The Image of an Artist

Parfume de Campange by Guy Begin
46
Fragrance Flavor Art Science

• The Perfumer An artist with a different palette

47
Fragrance Flavor Art Science

• Marketing- The Image

• The Allure of Perfume is popularized by marketing

48
Fragrance Flavor Art Science

• Marketing- The Image

• The Allure of Perfume is popularized by marketing

Zica-Alexa - Year 2000
49
Fragrance Flavor Art Science
OLFACTION GUSTATION
Multidisciplinary Fields

• Fragrances
• Perfume
• Soap/ Detergent /Air Fresheners / Aromatherapy

• Flavors Food Science
• Food Products
• Beverages
• Chewing Gum/ Mouthwash/ Pharmaceuticals
• Tobacco

50
Fragrance Flavor Art Science
OLFACTION GUSTATION
Multidisciplinary Fields

• Chemistry/ Biology/ Physiology/ Psychology
• - Organic Chemistry Synthetic, Molecular
  structure,
• Biochemistry, Molecular Biology, Genomics,
• Anatomy, Neuroscience, Bioinformatics
• - Analytical Chemistry GC-MS analysis,
  Quality
• Assurance
• - Physical Chemistry Emulsions, Light
  scattering, etc.
• - Psychological aspects of perception other
  influences

• Computer Science for all of the above

51
Fragrance Flavor Art Science
TASTE GUSTATION
Taste (Gustation) - sensitivity to substances in
solution
Taste Buds in epithelium of tongue, soft palate,
pharynx, larynx and epiglottis. 2000-5000 taste
buds in humans, but large variation.
52
Fragrance Flavor Art Science
TASTE GUSTATION

• Until the mid 1990s only 4 taste sensations
• were recognized
• Sweet e.g. Sucrose, Aspartame
• Sour e.g. Citric acid, Phosphoric acid (H
  ions)
• Bitter e.g. Quinine
• Salty Sodium Chloride

A 5th taste sensation called Umani is now
recognized. Most common example is MSG
(Monosodium glutamate) which enhances meat flavor.
53
Fragrance Flavor Art Science
SMELL OLFACTION
Smell (Olfaction) - sensitivity to substances in
gaseous phase - a distant sense
54
Fragrance Flavor Art Science
How We Smell -
Olfactory Region (Regio olfactoria)
Odorants are volatile chemicals carried by
inhaled air to the Regio olfactoria (olfactory
epithelium) located in the roof of the two nasal
cavities of the human nose, just below and
between the eyes. The olfactory region of each of
the two nasal passages in humans is a small area
of about 2.5 square centimeters containing in
total approximately 50 million primary sensory
receptor cells.
55
Fragrance Flavor Art Science

• New Technology How We Smell

Olfactory Nerve
Olfactory Bulb
Mitral Cell
Olfactory Tract
Glomerulli
Olfactory Nerve Filaments
Cribiform (bone)
Axons
Olfactory Epithelium
Olfactory Receptor Neurons
Cilia in Mucosa
Mucosa
Air and
Odorant Molecules
The olfactory region consists of cilia projecting
down out of the olfactory epithelium. The
olfactory cilia are the sites where molecular
reception with the odorant occurs and sensory
transduction (i.e., transmission) starts.
56
Fragrance Flavor Art Science

• New Technology Understanding Scent

Elucidation of Olfactory G-Protein Receptor
Structures - a result of Genome Research
Different Views of G-Protein Receptor Structures
900 Human Olfactory Receptor Genes Identified
D. Lancet 600 Pseudogenes 300 Intact Genes
57
Fragrance Flavor Art Science

• New Technology Understanding Scent

Putative Binding cavity in Human OR1.04.06
derived using CastP
58
Fragrance Flavor Art Science
Computer Modeling of New Odorants
Olfactophoric Model of Sandalwood
Odorants Javanol (Yellow) vs. beta-Santalol (Blue)
59
Fragrance Flavor Art Science

• New Technology Digital Scent

Hardware and software platforms for incorporating
scent into all forms of media... Peripheral
devices that recreate thousands of scents on
demand. Authoring tools for the creation of
"scent scores" for movies, music, and interactive
games. Software that plays scented media, such as
videos, music and DVD's. Systems for transmitting
scent with music and movies over the
Internet. Andfor the Perfumer Flavorist A
new tool for composing creations.
60
Fragrance Flavor Art Science
Flavor Research
The Proof is in the Pudding
Chefs and flavor application specialists determin
e use levels and food applications.